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PAPER

Nano scale investigation of particulate contribution

to diamond like carbon film by pulsed laser
Cite this: RSC Adv., 2016, 6, 6016
deposition
Madhusmita Panda,a G. Mangamma,a R. Krishnan,*a Kishore K. Madapu,a
D. Nanda Gopala Krishna,b S. Dasha and A. K. Tyagia

Received 14th October 2015
Accepted 4th January 2016
DOI: 10.1039/c5ra21361d
www.rsc.org/advances
Diamond like carbon (DLC) films were synthesized by a Pulsed Laser Deposition technique at room
temperature, with the laser pulse energy varying from 100 to 400 mJ. The films synthesized at different
pulse energies are labeled as DLC-100, DLC-200, DLC-300 and DLC-400. Due to laser ablation, the
DLC films contained a continuous phase and particulates embedded in it. These films were characterized
using X-ray Photoelectron Emission Spectroscopy (XPS), Raman spectroscopy based intensity mapping
and Atomic Force Acoustic Microscopy (AFAM). Carbon co-ordination inhomogeneity in DLC films was
monitored by intensity mapping of the Raman peaks. The average sp2 cluster size in the particulates was
calculated from the intensity ratio of the D and G peaks of the Raman spectra (ID/IG ratio) obtained from
the particulate region and was found to vary from 0.85 to 1.41 nm with various laser pulse energies.
Nanometric surface spatial elasticity distribution was mapped using AFAM, which revealed the presence
of nanoscale surface irregularities in all the DLC films. The number density of particulates in the present
DLC films is maximum in DLC-400 and minimum in DLC-100. Relative stiffness value of all the DLC films
with its particulate regions were determined and compared with respect to the relative stiffness of Si.
Raman spectroscopic intensity mapping and AFAM studies revealed that carbon co-ordination and local
elasticity distribution across the film and particulate of DLC films are observed to depend upon sp2
bonded carbons possessing different aromatic orders and sp3 content. The sp3 bonding content present
in DLC films synthesized at different laser pulse energies was obtained from X-ray photoelectron spectra.
DLC-300 was found to be the stiffest film (
4.5 times of Si) with highest sp3 content (53%).

mechanical properties like elasticity and hardness of the DLC

Introduction
DLC is one of the exciting and highly sought aer materials in
industrial applications due to its high hardness, high elastic
modulus, high electrical resistivity, good eld emission, high
thermal conductivity, high optical transparency and high
chemical inertness.1–4 DLC lms are commonly used for cutting
tools, anticorrosion coatings, tribological and electrochemical
applications, in addition to various other applications such as
protective layers in magnetic storage devices and micro-
electromechanical systems (MEMS).5–10 The properties of DLC
are inuenced by several features like; (a) sp3 content, (b)
H-content, (c) sp2 cluster phase, (d) sp2 cluster size, (e) number
density of sp2 cluster, (f) sp2 cluster phase orientation and (g)
any cross-sectional structure, as a consequence of interaction
among sp2 and sp3 bonding of carbon.11,12 The above mentioned
factors including chemical bonding of carbon atoms and
a
Materials Science Group, Indira Gandhi Centre for Atomic Research, Kalpakkam,
603102, India. E-mail: krish@igcar.gov.in
b
Corrosion Science and Technology Group, Indira Gandhi Centre for Atomic Research,
Kalpakkam, 603102, India
lms depend upon the deposition method and the parameters
used therein.1,2,13–17 This is because energy of carbon species
during deposition plays a vital role in establishing sp3/sp2 phase
formation in the DLC lms.1,2,13 Pulsed laser deposition (PLD)
has emerged as a successful deposition techniques to synthe-
size non-hydrogenated DLC (C–C sp2 and sp3 bonding) at room
temperature. During the deposition, particulate (
macro size)
formation occurs on the surface of thin lm due to heating of
subsurface area by incidence of high power density (
109 W
cm2) on the target surface. Presence of particulate inuences
the growth, morphology and surface mechanical properties of
thin lms. Particulate generation is more in Nd:YAG laser based
ablation than excimer lasers due to its higher wavelength,
which in turn make it more penetrating into the target surface.1
The presence of particulates changes the lm morphology and
consequently the roughness also increases. In PLD, the kinetics
and energetic of the plasma species produced by the laser
impact play an important role in the formation of DLC
lm.1,2,18–20 Quality of a DLC lm deposited by PLD depends
largely on energies and charge states of the ablated carbon
particles in the plasma plume.1,2 Research groups like Tabbal

6016 | RSC Adv., 2016, 6, 6016–6028 This journal is © The Royal Society of Chemistry 2016
Paper
et al., Yap et al. and Ruiz et al. have carried out studies on DLC
growth by PLD with parametric effects on its structural, optical,
electrical and mechanical properties. These studies aimed to
obtain high quality DLC lms for appropriate applications.2,14,18
Recently Ruiz et al. have studied elastic heterogeneities in
nanostructured DLC lms grown with various kinetic energies
of ions ablated with an Nd:YAG laser of 1064 nm wavelength.18
They have also studied sp3 content variation along the thickness
of the DLC lms by angle resolved X-ray photoelectron spec-
troscopy and observed that sp3 content is less on the surface as
compared to the subsurface region. They found that DLC lms
synthesized with lowest kinetic energy (100 eV) of carbon ions
with highest thickness (1050 nm) possess highest sp3 content
(40.8%) and all the lms have an elastic heterogeneity extend-
ing only to 20 nm diameter size domains. The thicknesses of
DLC specimens for higher kinetic energies (200 and 150 eV)
were 350 nm and 650 nm, respectively. All these factors make it
difficult to identify the dominant parameter (kinetic energy of
carbon ions or thickness) that contributes to sp3 content and
consequently to elasticity of the surface. Hence, in this paper we
have carried out a systematic study of DLC lm formation with
various laser pulse energies to obtain maximum sp3 content,
which will be suitable for hard coating related application. In
addition, Young's modulus (measure of stiffness/mechanical
property) of DLC lms has been reported to vary from
100–800 GPa and is a function of sp3 tetrahedral bonds in the
amorphous carbon network.21–23 Nano-indentation is a widely
used technique to determine the mechanical property of DLC
lms. However, in nano-indentation technique the maximum
penetration depth should be less than or equal to 10% of the
thickness to avoid any substrate effect, which can act as a limi-
tation in case of thin lms of few nanometers. Application of
DLC lms demands synthesis of lms with various thicknesses
starting from few nanometers to several micrometers. This
requirement makes the hardness and elasticity measurements
quite challenging. In this aspect, hybrid acoustic/AFM tech-
nique known as Atomic Force Acoustic Microscopy (AFAM) is
a promising surface specic tool to map elasto-mechanical
spread across a surface. This is a scanning probe microscopy
based nondestructive technique designed to map elasticity
distribution on a specimen surface.24–26 Since, thin lms grown
by PLD using 1064 nm wavelength laser pulse possess particu-
lates, it hinders local elastic mapping by AFAM at a constant
contact resonance frequency. Hence, to overcome this, point
spectroscopy method was adopted in AFAM to garner infor-
mation about relative stiffness of particulate interior and exte-
rior regions with respect to Si (111).
It is found from literatures, that many authors have adopted
the method of incorporating (elements such as N, F, Si or metal,
nanoparticles and nanocrystallites) at nanometric scale to
improve the physical, mechanical and tribological properties of
DLC for improved diverse applications.27–31 In PLD systems like
ours, which doesn't have sophisticated means for ltering
particulates, we should investigate the role of particulates
present in it, before incorporating such nanoparticles. Hence in
this report, evolution of carbon co-ordination in particulate
region and its contribution to surface elastic inhomogeneity of
This journal is © The Royal Society of Chemistry 2016
RSC Advances
DLC lms at nanoscale, which were synthesized at various laser
pulse energies, are probed. Study of surface elasticity variation
along the particulates and at regions are also mapped by AFAM
mode under optimized SPM operating parameters. In this
study, we have maintained most of the deposition parameters
like target (target–substrate distance), laser type, wavelength,
pulse duration, repetition rate and base pressure constant so as
to bring out the co-relation of laser pulse energy with kinetic
energy of carbon ions as reported earlier by Ruiz et al.18 This
approach enables one to undertake qualitative study of evolu-
tion of carbon co-ordination distribution, morphology and
surface elasticity inhomogeneity of nanostructured DLC lms
with particulates by two most sensitive and highly spatially
resolving techniques like Raman mapping and AFAM imaging.
These data were supplemented by quantitative analysis of sp3
content by X-ray photoelectron spectroscopy (XPS). A few
Raman imaging studies on DLC tribo lms, reported in the
literature, have already established it as a useful characteriza-
tion tool to nd out the phase change process (graphitization)
occurring during tribological sliding.32 We have also carried out
Raman mapping of G peak, D-peak and corresponding ID/IG,
respectively, by using a step size of 500 nm to obtain the local
co-ordination of carbon atoms.
Experimental section
A. DLC specimen synthesis by PLD
DLC lms were synthesized on silicon (111) substrates having
dimensions of 10  10 mm2 by pulsed laser ablation from high
pure graphite target with 10 000 laser shots. The Si substrates
were cleaned with lukewarm soap solution, deionised water,
acetone and ethyl alcohol for duration of 10 minutes per solvent
successively in an ultrasonicator bath to remove surface impu-
rities. The cleaned Si substrates were then loaded into laser
ablation UHV chamber. An Nd:YAG laser (M/s Quanta Systems,
Italy) operating at 1064 nm wavelength with maximum pulse
energy of 900 mJ, pulse width of 5 ns and a repetition rate of
10 Hz was used. The area of laser spot was 0.7 mm2. The depo-
sition process was initiated aer reaching a base pressure of 4.5
 106 mbar and the deposition was carried out at 6  106
mbar at room temperature. The substrate to target distance was
kept at 40 mm. The laser pulse energy was kept at 100, 200, 300
and 400 mJ for the synthesis of lms labeled as DLC-100, DLC-
200, DLC-300 and DLC-400 specimens, respectively. The depo-
sition of DLC lms were carried out by exposing the 200 diameter
pyrolytic graphite target (with purity close to 99.99%) to the
impacting laser pulses. Target was rotated continuously to
expose fresh surface and to prevent pinhole formation.
B. Characterization techniques
The thickness of the DLC lms was measured by a prolometer
(Dektak 6M stylus proler, M/s Veeco, USA). A 12 mm diameter
of spherical diamond tip was line scanned on the DLC lm
surface with a speed of 15 mm s1 to obtain the thickness. The
normal load on the tip and scanning length for each measure-
ment were 10 mg and 2000 mm, respectively.
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XPS experiments were carried out using a SPECS manufac- presence of particulates (
micrometers) restricts spatial elas-
tured (Germany) spectrometer employing monochromatic Al Ka ticity mapping with accuracy so we carried out the AFAM study
(1486.74 eV) as the primary excitation source at room temper- by mapping with magnitude of the coupled oscillation. Point
ature. The anode was operated at a voltage of 13 kV and the spectroscopy technique was used to determine the relative
source power level was set to 300 W. The spectra were collected stiffness of at surface and particulate with respect to Si (111).
using the PHOIBOS 150 MCD-9 analyzer with a resolution of In addition to AFAM, AFM images were also obtained between
0.67 eV for 656 kcps at pass energy of 10 eV and the data were the tip and the lm surface without any vibration.
processed by Casa XPS soware. The analysis of each of the
elemental carbon (1s) peak was deconvoluted aer the
subtraction of Shirley type background.
Results and discussion
Raman spectroscopy (inVia, Renishaw) studies were carried A. Thickness and roughness analysis
out in backscattering conguration with Ar+ laser excitation of Average thickness, rate of deposition and root mean square (rms)
wavelength 514.5 nm. This instrument is equipped with 1800 roughness with error obtained from surface prolometer and
lines per mm grating and a thermoelectrically cooled CCD AFM study, respectively, are shown in Table 1. It is observed from
detector. In the present study, Raman intensity imaging tech- Table 1 that thickness increases monotonically with laser pulse
nique was adopted along with the normal spectral acquisition. energy. Surface roughness (rms) of DLC lms increase with laser
A 100 objective with numerical aperture value of 0.9 was used pulse energy due to the reasons discussed here. Higher pulse
for collecting the spectra. The fully automated motorized energy extricates larger material ux resulting in higher growth
specimen stage (Renishaw M/S20), having a spatial resolution of rate and thickness; it also makes particulate emission more
100 nm, was used for the Raman intensity mapping. The Raman probable, thereby causing surface roughness to go up.
spectral mapping was performed by integrating intensities,
which is essentially the peak intensity distribution corre-
B. Compositional analysis
sponding to a particular wave number collected over a pre-
dened area.33,34 Mapping was carried out with a spatial scan- XPS analysis was used to obtain the sp3 content in the DLC
ning step size of 500 nm in a region of 4  3, 6  4, 4  2, and lms. Fig. 1 shows high resolution XPS spectra of carbon 1s
6  4 mm2 belonging to DLC-100, DLC-200, DLC-300 and DLC- (C1s) core level photoemission spectra from DLC lms synthe-
400 specimens, respectively, to include at least one particulate. sized at different laser pulse energies. The C1s XPS peaks were
Elasticity mapping was carried out using an advanced deconvoluted into three distinct Gaussian–Lorentzian peaks
multimode high resolution Scanning Probe Microscope (SPM) aer Shirley background correction (Fig. 2(a–d)) and these were
(NTEGRA Prima, M/s NT-MDT, Russia). A stiff cantilever was used for the estimation of sp3, sp2 and C–O bonding contents in
used in contact mode for AFAM study of DLC lms along with Si the lms.
as the reference. Both large area (5  5 mm2) and small area It is observed from Fig. 1 that the line shape and peak
(2.5  2.5 mm2) scans were carried out to observe the uniformity position of the C1s peaks vary with the laser pulse energy. The
and local structure of each lm. In addition, roughness
measurement was carried out using same cantilever tip. The
cantilever has a stiffness constant of 30 N m1 and dimension Table 1 Thickness and surface roughness (rms) from surface profil-
as 125  30  5 mm3. Resonance frequency of the cantilever is ometer and AFM study, respectively (errors within bracket)
about 330 kHz. In AFAM, the specimen was placed on the
Specimen Average Deposition rate RMS surface
specimen stage with an ultrasonic transducer beneath, it name thickness (nm) (nm per shots) roughness (Rq) (nm)
vibrated in the frequency range of 0–5 MHz. The cantilever
scans the specimen surface in contact mode through the tip. In DLC-100 105(3) 0.01(0.0003) 1.5(<0.5)
this technique, the mechanical boundary conditions are guided DLC-200 120(5) 0.012(0.0005) 2.7(<0.5)
DLC-300 144(12) 0.014(0.0012) 3.3(<0.5)
by two kinds of interactions. First, interaction is nonlinear
DLC-400 169(13) 0.017(0.0013) 4.5(<0.5)
contact mode function of distance, which is due to mutual
interaction between the tip and the lm surface devoid of
vibration. It becomes attractive at larger distances, becomes
repulsive when the tip is in contact with the surface and
increases rapidly when the tip is pressed against the specimens.
Second, the longitudinal acoustic wave emitted from the
transducer impacts the specimen which causes out-of-plane
vibrations on the specimen surface leading to change in the
mechanical boundary conditions. The surface vibrations are
transmitted into the cantilever via the sensor tip. Photo diode
and a lock-in-amplier are used to measure and evaluate the
cantilever vibrations. Coupled modes of vibration specic to
surface elasto-mechanical response are measured and a spatial
elasticity map is eventually generated.25,26,35,36 In our study, Fig. 1 XPS C1s peak for DLC specimens at various laser pulse energies.

6018 | RSC Adv., 2016, 6, 6016–6028 This journal is © The Royal Society of Chemistry 2016
Paper
line shape asymmetry stems from contribution of various
chemical environments arising out of different hybridization
states of carbon. The C1s peak position shis towards higher
binding energies and its shape tends to become more
symmetric for DLC-300 specimen, indicating the trans-
formation of sp2 sites into sp3 sites. The C1s peak position at
lower binding energies and its asymmetric shape for DLC-100,
DLC-200 and DLC-400 specimen indicate lower sp3 content.
Fig. 2 shows the deconvoluted spectra of C1s peaks of DLC
lms deposited at different laser pulse energies. The rst peak
Fig. 2 XPS C1s peak de-convolution for (a) DLC-100, (b) DLC-200, (c)
DLC-300 and (d) DLC-400 films.
This journal is © The Royal Society of Chemistry 2016
RSC Advances
is located at 284.4  0.1 eV and corresponds to sp2 hybridized
state of carbon atoms. The second occurs at a higher binding
energy of 285.2  0.1 eV and corresponds to sp3 hybridized state
of carbon atoms. The observed peak positions in the present
study matches with the values reported in the literature for PLD
grown DLC lms.2,37 The third peak at the binding energy value
of 286.2  0.1 eV is due to C–O (or C]O) bond dominated
chemical environment.38 Fractions of sp2 and sp3 hybridized
carbon atom are estimated from the ratio of the corresponding
peak area to the total C1s peak area and tabulated in Table 2.
Voevodin et al. reported that the sp3 content of DLC lms
deposited by Nd-YAG laser is low.1 The observed relatively low
sp3 content of the coatings in the present study is in agreement
with Voevodin's observation. These observations point towards
the growth of graphitic lms and entrainment of particulates
emitted by PLD process which employs 1064 nm Nd:YAG laser
radiation at laser pulse power densities $109 W cm2. Opti-
misation of the pulse energy to form DLC lms leads to the
conclusion that 300 mJ laser pulse energy is around the
threshold energy to obtain a DLC lm with maximum sp3
content (53.47%). This observation is comparable to the study
of Ruiz et al.18
From Table 2, it is clear that DLC-100 and DLC-200 speci-
mens have sp2 as the dominant phase fraction. This may be due
to less kinetic energy of carbon ions in the plasma in compar-
ison to threshold energy. However, there is a complete change
of scenario in DLC-300 specimen, where sp2 makes up only
a fraction of 38.25% and sp3 becomes 53.47%. The sp3 content
in DLC-400 specimen is found to be similar to that of DLC-100
and DLC-200 specimens. Earlier studies on PLD grown DLC
have indicated that the charge state and kinetic energy of
carbon ions in the plasma plume determine the carbon co-
ordination in thin lm.1,19,39 The sudden increase of sp3
content in DLC-300 specimen is understandable with respect to
sub-plantation theory. According to this theory, when kinetic
energy of carbon ions in the plasma exceeds threshold energy, it
penetrates into the thin lm surface to achieve a dense lm with
substantially higher sp3 content.18
As shown in Table 2, the C and O bonding contribution is
higher in DLC-300 as compared to DLC-100, 200 and 400
specimens. This indicates that the carbon dangling bonds in
DLC-300 may more, which makes bonding with atmospheric
oxygen during exposure. In case of DLC-100 and DLC-200
specimens, it can be predicted that lower energetic carbon
ions in the plasma plume sticks to the surface without pene-
trating into the lm and contribute more towards sp2 bonding
in the lms. In case of DLC-400 specimen, though the laser
uence is highest which means that the plasma contains higher
energetic and charge states of carbon species, it still has
sp3-content similar to that of DLC-100 and DLC-200 specimens
indicating that it does not follow the subplantation theory.39
Hence, it can be speculated that the total kinetic energy of
carbon ions in DLC-400 is not used to implant the ions in the
subsurface of the thin lm as in case of DLC-300. A fraction of
the kinetic energy of carbon ions is used for other processes,
like local heating due to dissipation of excess energy, following
the thermal spike model causing sp3 to sp2 phase
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Table 2 XPS C1s spectra de convolution results (errors within bracket)

Specimen sp3 band sp2 band C–O band C–O

3
name position sp FWHM position sp2 FWHM position C–O FWHM sp3 (%) sp2 (%) (or C]O) (%)

DLC-100 285.3(0.1) 1.0 284.5(0.1) 1.1 286.3(0.1) 1.3 32.3(5%) 63.7(5%) 4.0(5%)
DLC-200 285.3(0.1) 0.9 284.4(0.1) 1.1 286.0(0.1) 1.4 29.1(5%) 65.4(5%) 5.5(5%)
DLC-300 285.2(0.1) 1.1 284.3(0.1) 1.0 286.4(0.1) 1.4 53.4(5%) 38.3(5%) 8.3(5%)
DLC-400 285.2(0.1) 1.0 284.4(0.1) 1.0 286.0(0.1) 1.5 30.5(5%) 63.9(5%) 5.6(5%)

transformation.2,18 In addition, at higher laser pulse energies
the particulate ejaculation is high, which hinders evolution of
sp3 phase as the graphitic matrix is retained as sp2 phase on the
lm surface.1,19 Hence, it can be said that both the above
mentioned phenomena have a combined effect on the lm
formation at 400 mJ.
In the following section, we have undertaken two mapping
characterization techniques viz.; visible Raman spectroscopic
intensity mapping for local co-ordination and aromaticity of sp2
bonded carbons in the particulates as well as on the surface and
AFM morphology along with AFAM magnitude imaging for local
elasticity distribution on surface to understand the XPS result
by nanometric evolution process.
C. Structural analysis
Raman spectroscopic imaging over the DLC lm surface with
a spatial scanning step size of 500 nm for determining local co-
ordination of carbon in at and particulate regions was carried
out. Fig. 3(a–d) shows the optical images of the mapped area on
the surface of all DLC lms and the mapped area including
particulate is shown as inset.
During the scanning, laser power was kept low (<1 mW) to
prevent laser induced damage of the specimen. The pre-selected
area is different for different lms (8–24 mm2); hence number of
acquired spectra varied from lm to lm.
Fig. 3Optical microscope images of (a) DLC-100, (b) DLC-200, (c)
DLC-300 and (d) DLC-400 (inset – magnified image of mapped area).
All the mapped spectra corresponding to the DLC lms were
individually background subtracted and one of the Raman
spectra obtained from the particulate region was deconvoluted
into two Gaussian peaks corresponding to two distinct vibra-
tional modes (G-band and D-band) of sp2-bonded carbon
atoms. Usually the Raman spectra of disordered graphite
exhibit two modes, the G peak (stretching mode) around 1550–
1600 cm1 and the D peak (breathing mode) around 1355 cm1,
which are assigned to zone centre phonons of E2g symmetry and
K-point phonons of A1g symmetry, respectively.4,11,40–42
Nanocrystalline and amorphous carbon phases are charac-
terised by the position, intensity and width of the G and D peaks
in the Raman spectra. The G peak at 1581 cm1 represents
graphitic phase corresponding to E2g symmetry and is associ-
ated with the in-plane bond-stretching motion of pair of sp2
bonded carbon atoms. This mode does not require presence of
six fold ring and is present in all sp2 sites. The G band in the
range of 1500–1630 cm1 corresponds to sp2 sites in aromatic
and olenic molecules.4,11,43 The blue shi in G peak is due to
smaller aromatic clusters having higher modes.4,11,44 In addi-
tion, decrease in number of ordered aromatic rings on passing
from nanocrystalline graphite to a-C also contributes to the blue
shi of G-peak. It also reduces D peak intensity due to soening
of the vibrational density of states.4,11,45 Due to the higher
sensitivity of visible Raman spectroscopy (50–230 times)
towards sp2 bonding than UV Raman spectroscopy, it is used as
an indirect probing tool for sp3 content.4,46,47 In the following
section, structural evolution of particulate region and their
contribution to the DLC lm with laser pulse energy variation
are discussed.
Structural analysis of only particulate region on DLC lms.
In this section, structural evolution of particulate region and
their contribution to carbon co-ordination on the lm with laser
pulse energy are discussed. Fig. 4(a–d) shows all the deconvo-
luted spectra obtained from the particulate regions. Peak
position, FWHM of G and D peaks, ID/IG ratio, cluster size
(effective crystallite size in the direction of graphite plane) and
ID/IG ratio obtained from Raman spectroscopic mapping are
tabulated in Table 3. ID/IG ratio of Raman spectra obtained from
the particulate region was used in Tuinstra and Koenig (TK)
equation for second stage (nanocrystalline graphite to a-C) of
amorphization trajectory to calculate the cluster size (L) in the
DLC lms.4,11,48 The TK relations for second stage of amorph-
ization trajectory is given as follows:
ID
¼ CðlÞL2 (1)
IG

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Paper RSC Advances

regions.44 The decrease of D-peak intensity in the shoulder

Fig. 4 Deconvoluted Raman spectra obtained from particulate
regions of (a) DLC-100, (b) DLC-200, (c) DLC-300 and (d) DLC-400
films.
C(l) is a constant and depends on the laser wavelength used for
excitation (514.5 nm) and is 0.55 nm2. It is clear from the Table
3, that DLC-300 has the smallest sp2 cluster (0.74 nm)
embedded in the particulate region. This indicates that the sp2
bonding of carbon atom in the particulate region of DLC-300 is
more of chain type. However, particulate region of DLC-100,
DLC-200 and DLC-400 possess higher cluster sizes 1.23, 1.28
and 1.34 nm, respectively. This indicates that the sp2 bonding of
carbon atom in the particulate regions of DLC-100, DLC-200
and DLC-400 is in aromatic rings. Small cluster volume
possibly arises from the presence of compressive stress.
From deconvoluted spectra, it is found that the G-peak for all
the DLC lms lies in the range 1553–1580 cm1, which is lower
than that of the G-peak of graphite (1581 cm1). It is observed
from Fig. 4(a, b and d) that D-peak starts appearing at 1379,
1410 and 1416 cm1 in DLC-100, DLC-200 and DLC-400 lms,
respectively, with skewness associated with the G-peak.
According to the report of Mapelli et al., the upward shi of
D-peak and presence of intense D-peak as a prominent shoulder
in DLC-200 and DLC-400 clusters specimen indicate occurrence
of large number of aromatics entrained in the particulate
region and wave number shi towards a lower value 1360 cm1
in DLC-300 concludes that the particulate region of DLC-300
possess as either reduced number of ordered aromatic rings
or more number of olenic carbon chains consisting of sp2
bonds, which is in concurrence with the report of Beeman
et al.45
The relation between G-peak, D-peak and ID/IG ratio for the
individual peaks obtained from particulate region is shown in
Fig. 5. According to the amorphous trajectory (graphite /
nanocrystalline graphite / a-C / TAC), G-peak position and ID/
IG ratio from individual spectra (particulate region) of DLC-300
lie in the third stage of amorphization trajectory. This indi-
cates that particulate region on DLC lms are amorphous in
nature with higher sp3 content (>20%).11 Fig. 6 shows the rela-
tionship between full width at half maximum (FWHM) of G-peak
and ID/IG ratio obtained from the particulate region of DLC lms
at various laser pulse energies and the sp3 content obtained from
XPS study. FWHM of G-peak and sp3 content of carbon shows
similar trend whereas ID/IG ratio shows reverse trend, which also
corroborates the fact that suddenly, sp3 content increases with
densication and amorphization at 300 mJ following sub-
plantation theory for formation of DLC lms and fails above it
due to dissipation of the extra energy to the surrounding. The
dissipation of extra energy in DLC lms leads graphitization
(conversion of sp3 to sp2 bonding).18 The slight fall of sp3 content
Fig. 5 Relation among G-peak, D-peak position and ID/IG ratio ob-
tained from particulate regions of DLC films at various laser pulse
energies.

Table 3 Raman spectra deconvolution results and cluster size obtained from ID/IG ratio of deconvoluted spectra and Raman spectroscopic
mapping data of the DLC film

Mapping data

Specimen G-peak position G-peak FWHM D-peak position D-peak FWHM ID/IG (peak Cluster size ID/IG ID/IG ID/IG
name (cm1) (cm1) (cm1) (cm1) intensity ratio) (nm) total at particulate

DLC-100 1560 190 1379 325 0.7 1.13 0.54–0.64 0.54–0.58 0.54–0.64
DLC-200 1568 180 1410 360 0.9 1.28 0.50–0.66 0.60–0.65 0.50–0.58
DLC-300 1553 213 1360 287 0.4 0.85 0.38–0.45 0.38–0.44 0.42–0.46
DLC-400 1580 135 1416 338 1.1 1.41 0.60–0.75 0.60–0.72 0.65–0.75

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RSC Advances
Fig. 6 Relation among FWHM of G-peak, ID/IG (particulate region) and
sp3 content (XPS) of DLC films at various laser pulse energies.
for DLC-200 is the contribution from bigger size particulates
than DLC-100. To study the contribution of particulate regions to
DLC lms, Raman spectroscopic intensity mapping was carried
out and this is discussed in succeeding section.
Structural analysis of DLC lm (including particulate
region). The Raman intensity mapping of G and D peak (ob-
tained from deconvolution), and corresponding ID/IG ratio
mapping for DLC-100, DLC-200, DLC-300 and DLC-400 speci-
mens are shown in Fig. 7(a–d). It is observed from G, D and ID/IG
ratio mapping that there is an intensity contrast from at to
particulate region in all DLC lms. Here, it is focused on ID/IG
ratio map of all DLC lms, which provide the information about
the presence of aromatic rings/chain type structures of sp2
bonding in clusters as discussed earlier. In addition, qualitative
analysis of sp3 content and density of DLC lms across its
particulate regions with various laser pulse energies is also
deduced from ID/IG ratio mapping.
According to Kelires et al., a local compressive stress is
induced during deposition process due to high energetic ion
bombardment, along with the shallow implantation (‘sub-
plantation’) of incoming atoms.49 As a consequence, transition
from sp2 rich phase to stabilised sp3 rich phase takes place at
a critical compressive stress value (
4–5 GPa). However, J.
Robertson stated that, energy of ion is responsible for sub-
plantation, producing densication of the lm thus promoting
sp3 content. Densication is the causative factor for evolution of
compressive stress.50
ID/IG ratio map of Fig. 7(a) reveals that particulate region of
DLC-100 specimen possesses ID/IG ratio in the range 0.54–0.64
(violet-red colour) with a gradually increasing manner from
centre towards the at region having a lower range 0.54–0.58
(blue-black colour). Most of the at regions correspond to ID/IG
ratio (0.54–0.60). The above mentioned result illustrates that
particulate region possess smaller sp2 bonded aromatic carbon
clusters (1.13 nm) with similar sp3 content of the at surface
and embedded in it.11,50 In other words, it can be stated that the
particulate regions possess similar compressive stress to the at
surface, which promotes densication as well as enhancement
in sp3 content.49,50
ID/IG ratio map of DLC-200 specimen shown in Fig. 7(b)
reveals particulate region exhibit similar contrast as the
6022 | RSC Adv., 2016, 6, 6016–6028
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particulate region of DLC-100. In fact, the at region has
a variation in the higher range 0.50–0.65. Since, the particulate
region of DLC-200 specimen have lower ID/IG value (0.50–0.58)
with respect to the at region, there is indication that smaller
sp2 bonded aromatic carbon cluster (1.28 nm) has
a pronounced occurrence in these particulate regions than the
at region. ID/IG ratio map of the at surface reveals a non-
uniform distribution pattern. This pattern indicates that the
particulate region and at surface are under non-uniform
compressive stress but with different value.11,50 As a result
densication and sp3 content varies accordingly.
ID/IG ratio map of DLC-300 specimen is shown in Fig. 7(c).
This reveals particulate region possesses the range 0.42–0.46 of
intensity map. There is a gradual decrease of ID/IG ratio starting
from the centre of the particulate region towards the at region
which indicates presence of uniform compressive stress and
densication.11,50 The at region of DLC-300 specimen has an
ID/IG ratio value in the low range (0.38–0.44). Though in DLC-
300 the particulate regions have higher ID/IG ratio value with
respect to the at surface, but it is less as compared to DLC-100
and DLC-200 specimens. This indicates that the particulate
region of DLC-300 specimen has larger aromatic clusters
(cluster size
0.85 nm) than the corresponding at surface,
which is smaller than DLC-100 and DLC-200 specimens. The ID/
IG ratio for both at and particulate regions of DLC-300 reveals
that sp3 content is more in comparison to DLC-100 and DLC-
200 specimens.
ID/IG ratio map of DLC-400 specimen is shown in Fig. 7(d). It
reveals that the particulate region possess the intensity
contrasts (0.65–0.75) in such a manner that the maximum (red
colour) ID/IG value lies at the centre of the particulate region and
it decreases gradually towards the at surface (0.60–0.72). The
higher ID/IG value of particulate region indicates that it has
bigger aromatic sp2 clusters (1.41 nm) with lower sp3 content
and density.11,50 The at surface shows a similar pattern like
DLC-200 specimen having lowest ID/IG value (0.60–0.72). The
very high value of ID/IG on the at surface indicates that DLC-
400 has higher aromatic sp2 clusters with less sp3 content and
density on the at surface as compared DLC-100, DLC-200 and
DLC-300. In DLC-400 both at surface and particulate region
possess bigger sp2 clusters than other DLC specimens, which
decreases its sp3 content and it's density.
D. Surface elasticity distribution analysis
We have carried out local elasticity mapping of each specimen
using AFM in contact mode as described in the Experimental
section. Prior to the experiment, AFAM imaging was carried out
on “Si (111)” for reference. The large area (5  5 mm2) scan was
done to see the uniformity of each DLC lm and small area
(2.5  2.5 mm2) scan was carried out to observe the local
structures present within the lm. These results were compared
with “Si” for morphology as well as AFAM imaging. Fig. 8
depicts AFAM signal as magnitude (Mag), M$Cos (magnitude 
Cos) and phase along with AFM topography of Si substrate.
More than one signal, M$Cos (magnitude  Cos) is employed to
improve the ner details present in the AFAM image. Si surface
This journal is © The Royal Society of Chemistry 2016
Paper RSC Advances

Fig. 7 Raman mapping image for G-peak, D-peak and ID/IG of (a) DLC-100, (b) DLC-200, (c) DLC-300 and (d) DLC-400, respectively.

This journal is © The Royal Society of Chemistry 2016 RSC Adv., 2016, 6, 6016–6028 | 6023
RSC Advances
Fig. 8 AFM topography (height) and AFAM (Mag, M$Cos and phase) images of Si (111) for small and large areas, respectively.
has an average roughness of
1 nm and AFAM mapping clearly
shows nano-micro-inhomogeneity with respect to local elas-
ticity contrast.
AFM morphology and AFAM image (Mag) of all DLC lms for
both small area (2.5  2.5 mm2) and large area (5  5 mm2) scans
are shown in Fig. 9(a–d) for DLC-100, DLC-200, DLC-300 and
DLC-400 specimens, respectively. The magnitude variation is
observed as dark and bright regions. The large change in the
Mag image is mainly due to various types of particulate regions
with different mass, size and shape distribution on the DLC lm
surface. This is attributed to discrepancy in elasticity among
different particulate regions, their boundaries and also associ-
ated structures entrained within them. The purpose of this
study is to determine surface elastic forces on at surface and
particulate region of DLC lms. The expression for stiffness (K*)
of the coupled oscillator system can be written as;25,26,35,36,51
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 
K* ¼ 3 6RFE*2
where, F, R and E* are the applied static force, radius of the
sensor tip and the elastic constant of the tip and the specimen,
respectively. E* is given as follows:
1 1 1 size particulates. It has been conrmed from XPS that DLC-200
¼ * þ *
E* Etip Especimen
Etip Especimen
*
where, Etip ¼ ; E* ¼ . Here, “ntip”
ð1  ntip 2 Þ specimen ð1  nspecimen 2 Þ
and “nspecimen” represent Poisson's ratios of tip and specimen,
respectively.
The AFAM methodology uses contact resonance spectros-
copy. When the cantilever tip comes in contact with the stiff
region of the specimen surface, the frequency and amplitude of
contact resonance curve gets enhanced while the FWHM
decreases. The opposite happens when the tip is brought in
contact with soer region. Hence, the choice of the operating
frequency causes appropriate contrasting features to be
6024 | RSC Adv., 2016, 6, 6016–6028
Paper
exhibited. Operating frequency having a value higher than the
resonance value causes stiffer region to appear bright and
consequently soer region appears dark. However, if the oper-
ating frequency is lower than resonance frequency, a contrast
inversion takes place causing stiffer region to appear dark and
vice versa. This AFAM formalism is used to discriminate hard
and so regions.36
Mag image of Fig. 9(a) for DLC-100 specimen illustrates an
elasticity contrast, where the soer regions are dark and the
stiffer regions are bright. The contrasting features in DLC-100
specimen reveal two different observations. Contrast between
smaller particulates and bigger particulate regions are clearly
observed due to dissimilar relative stiffness values. This
happens due to variation in densities and entrained subspecies.
Hence, AFAM image specically illustrates very small
discrepancy in mechanical properties within small areas. The
roughness of DLC-100 specimen obtained from AFM study is 1.5
(2) nm.
Mag image of DLC-200 specimen is shown in Fig. 9(b). It
shows that DLC-200 has soer regions as compared to that of
DLC-100 which corresponds to dark region. This is owing to the
increased laser pulse energy which enables ablation of higher
(3)
has a higher sp2 contribution than DLC-100. Since, DLC-200 has
bigger particulates than DLC-100 as shown in Fig. 9(b). There-
fore, it can be inferred that the occurrence of bigger particulates
will lead to a higher sp2 contribution. In addition, it is observed
from AFM study that DLC-200 specimen has a higher surface
roughness (2.7 nm) as a result of bigger size of particulate.
Fig. 9(c) and (d) show number of particulates along with at
surface for DLC-300 and DLC-400 specimens, respectively. The
roughness values of the DLC-300 and DLC-400 specimens ob-
tained from the AFM study were found out to be 3.3 and 4.5 nm,
respectively. This increase in roughness with laser pulse energy
can be attributed to the presence of larger extent of so zones as
This journal is © The Royal Society of Chemistry 2016
Paper
Fig. 9 AFM topography and AFAM (Mag) images for small and large area of (a) DLC-100, (b) DLC-200, (c) DLC-300 and (d) DLC-400,
respectively.
seen in AFAM images. In addition, it is also observed from
Fig. 9(c) and (d) that the number of so zones increases with
increase in pulse energy. Therefore, DLC-400 has a higher
number density of so zones in comparison to DLC-300.
Hence, it can be inferred that the dominance of so phase
brings down the relative stiffness value. The height contrasted
AFM image has numerous contrasting features depicting
spherically shaped particulate regions. The AFAM image is
dominated with large number of elastically so zones which
eventually depresses the relative stiffness value. The contact
resonance frequency of Si with known elastic constants and
Poisson ratio was measured prior to commencing the
measurements on the DLC specimens for contact resonance
frequency and relative stiffness values. Mathematical
This journal is © The Royal Society of Chemistry 2016
RSC Advances
expression for the contact resonance frequency of the coupled
oscillator system is given by eqn (4),25,26,35,36,51
sffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
K* þ Kc
f ¼ f0 (4)
Kc
where f0 is free oscillation frequency of the cantilever, K* and Kc
are stiffness of coupled oscillator system and the tip,
respectively.
In this study, point spectroscopy method was adopted to
avoid hindrances in set values during measurement of contact
resonance frequency. This was necessitated due to the presence
of particulates in DLC lms. The relative stiffness of Si (111) and
DLC-100, DLC-200, DLC-300 and DLC-400 specimens were
calculated from the contact resonance frequency of cantilever.
RSC Adv., 2016, 6, 6016–6028 | 6025
RSC Advances
Table 4 Contact resonance and relative stiffness value of DLC films
Specimen Relative stiffness Resonance frequency shi (kHz)
Si 1.02 1025.8
DLC-100 2.3 (on particulate) 1120 (on particulate)
1.8 (on at region) 1116.1 (on at region)
DLC-200 1.7 (on particulate) 1093.05 (on particulate)
2.2 (on at region) 1108.74 (on at region)
DLC-300 1.0 (on particulate) 967.43 (on particulate)
4.6 (on at region) 1165.0 (on at region)
DLC-400 0.4 (on particulate) 953.0 (on particulate)
0.5 (on at region) 957.13 (on at region)
These values are listed in Table 4. The relative stiffness and
contact resonance frequency of each lm have been measured
with respect to standard specimen Si (111). Table 4 depicts the
behavior of relative stiffness variation on particulate regions
and at surfaces of DLC lms with respect to laser pulse energy.
The relative stiffness on at surface of all DLC lms except DLC-
400 specimen has a higher value than that of Si (1.02). DLC-300
has the maximum value of relative stiffness (<4.5818). In case of
DLC-300 specimen, relative stiffness of at region is 4.5 times
higher than that of Si.
In case of DLC-100 specimens, particulate regions (2.3) show
higher relative stiffness than that of at region (1.8). This value
is almost doubled with respect to Si. DLC-200 specimens show
reverse trend as compared to DLC-100 specimen, which yielded
higher relative stiffness on at surface (2.2) as compared to
particulate surface (1.7). DLC-400 has lower relative stiffness on
at surface and particulate region as compared to Si. This can
be attributed to the presence of bigger particulates resulting in
high density of defects as reported by Mangamma et al.36
Contact resonance frequency of the cantilever on Si was
measured each time before measuring the same on DLC lms.
This was done to achieve calibration of cantilever with respect
to Si. Flat surfaces of all the DLC lms (1116.1, 1108.74 and
1165.0 kHz) except DLC-400 specimen (957.13 kHz) have higher
contact resonance frequency in comparison to Si substrates
(1025.8 kHz). This indicates that at surface of all DLC speci-
mens (except DLC-400) have higher relative stiffness values than
Si. In fact DLC-300 has relative stiffness 4.5 times of Si. DLC-400
specimen has a very low value of relative stiffness (0.5). Partic-
ulate regions of DLC-100 (1120 kHz) and DLC-200 (1093.05 kHz)
have higher contact resonance frequencies with respect to Si,
whereas DLC-300 (967.43 kHz) and DLC-400 (953.0 kHz) possess
lower values. The observed relative stiffness in case of particu-
late regions of DLC-300 and DLC-400 lms indicate that these
are soer than those present in Si. Particulates of DLC-100 and
DLC-200 lms have higher relative stiffness with respect to Si
but for DLC-300 and DLC-400, it is less than that of Si. All the
relative stiffness results experimentally measured pertain to
contribution from particulate number density and their size
distribution across the surface. These aspects cause modica-
tion in contact stiffness of the cantilever.
Generally particulates are soer than the at region of the
DLC lms, because particulates are mostly made up of sp2
6026 | RSC Adv., 2016, 6, 6016–6028
Paper
clusters which are loosely packed in particulates than the at
surface. Again density of particulate varies with it's size, which
affects it's stiffness. We observed that as the particulate size
increases from DLC-1 to DLC-4, the measured relative stiffness
decreases in the same manner indicating the decrease of
density.
AFAM results of DLC lms are similar to that of Raman
mapping data. Relative stiffness of particulate regions and at
surface can be explained on the basis of aromaticity of sp2
bonded carbons, cluster size, sp3 content and density, as sup-
ported by Raman mapping and XPS studies. From Table 2, it is
clear that thickness of a DLC lm increases with increase in
laser pulse energy, which in turn increases the density of DLC
lms and as a result relative stiffness should increase with laser
pulse energy.49 However, AFAM study of at surface of DLC lms
reveals that the relative stiffness increases up to 300 mJ and
above this, it shows a decline. XPS study shows a deviation from
subplantation model for DLC-400 specimen having 30% sp3
content. DLC-300 specimen has highest sp3 content of 53%. In
addition, the evolution of ID/IG ratio (chain type/aromatic rings)
and shi in G-peak position (cluster size) with laser pulse
energy follow the same trend in line with the ndings from
AFAM and XPS.
Fig. 7 reveals that, as seen from ID/IG ratio, all specimen,
except DLC-400, follow the subplantation theory.39 Hence, DLC-
100 specimen all others possess higher ID/IG ratio for particulate
region than at surface. Similar result is also obtained from
AFAM study. The particulate regions of DLC-100 specimen are
stiffer than its at surface, whereas the at surfaces of other
samples are stiffer than their particulate counterparts. This
result is due to synergetic effect of density (size dependent),
entrained substructures (clusters) and disorderedness (chain
type or aromatic rings of sp2 cluster) within the particulate
regions, which is a consequence of intrinsic stress acquired
during deposition. Crystalline diamond has only sp3 bonding,
which is very strong as a result diamond is hard. Whereas in
polycrystalline diamond, grain boundaries instigate some sp2
sites and other p-bonding states and introduces optical
absorption subgroups. The stiffness depends on the fraction of
C–C sp3 sites, as only the sp3 sites contribute signicantly to the
hard zones. In DLC, both sp3 and sp2 sites are present, which
renders its electronic structure fundamentally different to ideal
diamond.
The sp2 sites have an inclination to form clusters to lower
their free energy. DLC (or ta-C with lower C–C sp3 content) is an
atomically disordered alloy of sp2 and sp3 sites where the sp2
sites are not strongly clustered. In this way, the density is line-
arly proportional to the sp3 content as seen through experi-
mentally and corroborated by earlier theoretical calculations.
Hence higher C–C sp3 fraction in DLC makes the material closer
to diamond in terms of mechanical properties as revealed from
AFAM, XPS and Raman spectroscopic studies. Both density and
stiffness of lms can be explained in terms of phase fraction of
sp2 and sp3 types of carbon co-ordination.
The behaviour observed for DLC lms with various laser
pulse energies can be attributed to the synergistic effect of two
factors, viz.; (a) dissipation of extra energy (above threshold
This journal is © The Royal Society of Chemistry 2016
Paper
energy
300 mJ) to the surrounding resulting transition of sp3
to sp2 bonding (graphitization process) and (b) number density
and size of particulate regions entrained in each lm.
Conclusion
DLC lms of varying sp3 content were synthesized at various
laser pulse energies (100–400 mJ) with steps of 100 mJ. Quan-
titative and qualitative studies of sp3 content were deduced
from XPS and Raman spectroscopy, respectively. XPS study
revealed that DLC-300 possesses highest sp3 content (53%),
whereas other DLC lms possess a sp3 content of
30%. In our
study, the evolution of sp3 content follows the subplantation
model up to DLC-300 and fails for energies beyond it. The
average cluster size calculated from ID/IG ratio obtained from
the particulate region varies with laser uencies as 1.13, 1.28,
0.85 and 1.41 nm. The relative stiffness constants of all DLC-
lms (except DLC-400) are more with respect to Si, which
indicates that DLC-400 is very so. In case of DLC-300 the
relative stiffness is very high as compared to Si, which is about
4.5 times higher but the bigger particulate regions are very so.
It is observed that 300 mJ laser pulse energy is the threshold
energy for obtaining highest sp3 content and relative stiffness. It
is also found that the bigger particulate regions are so in
comparison to small ones owing to poor density and higher
number of defect states. In this study, it has been pertinently
pointed out that AFAM is an effective technique to nd out the
nanoscale mechanical property.
Acknowledgements
We would like to acknowledge Dr Sandip K. Dahara, Mr Avinash
Patsha and Ms Madhusmita Sahoo, Material Science Group,
IGCAR, Kalpakkam, for their kind help in experiment, data
analysis and useful suggestions, respectively.
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